The present invention relates to mixtures of manganese complexes and organic ligands which significantly improve the bleaching effect of hydrogen peroxide in washing liquors and which prevent the reabsorption of migrating dyes in peroxide-containing washing liquors, to washing and cleaning agent formulations containing said mixtures, and to methods using such washing and cleaning agent formulations for cleaning and/or bleaching substrates and for preventing the reabsorption of migrating dyes in washing liquors.
Peroxide-containing bleaches have been used in washing and cleaning processes for some time. At a liquor temperature of 90xc2x0 C. or more they are highly effective. As the temperature drops, however, their performance decreases markedly. It is known that diverse transition metal ions, added in the form of suitable salts or co-ordination compounds containing such cations, catalyse the degradation of H2O2. In this way it is possible to increase the bleaching effect of H2O2, or of precursors releasing H2O2 and also of other peroxide compounds, which effect is insufficient at lower temperatures. Important in practice are in this case only those combinations of transition metal ions and ligands, the peroxide activation of which is also expressed in an enhanced readiness to oxidise with regard to the substrate and not only in a catalase-like disproportionation, for the latter activation, which is unwanted in the present case, can further diminish the bleaching effects of H2O2 and its derivatives which are insufficient at low temperatures.
As regards bleaching-effective H2O2 activation, mono- and polynuclear variants of manganese complexes with diverse ligands, in particular with 1,4,7-trimethyl-1,4,7-triazazyclononane and, optionally, oxygen-containing bridging ligands, are held at present to be particularly effective. Such catalysts are sufficiently stable under practice conditions and contain the ecologically safe metal cation Mn(n+). However, their use entails substantial damage to dyes and fibres.
Surprisingly, it has now been found that in the case of certain manganese complexes the specific effect (i.e. the effect per mol of manganese complex) as catalysts for bleaching substrates and for preventing the reabsorption of migrating dyes in peroxide-containing washing liquors can be markedly enhanced if the manganese complex is mixed with a 0.2 to 50-fold molar amount of one or more than one organic ligand having a low molecular weight and if this mixture is used as catalyst in the washing process. This results in a synergistic effect between certain manganese complexes and certain organic ligands, not just in a simple addition of the individual effects: There are ligands which do not have any catalytic effect themselves but which can markedly enhance the specific catalytic effect of certain manganese complexes in a mixture. The catalytic effect per gramme of catalyst is then higher for the mixtures than for the pure manganese complexes and the risk of potential damage to dyes and fibres is reduced. In addition, the amounts of manganese required are smaller. Furthermore, mixtures of a manganese complex and the chemically corresponding ligand can be easily prepared by adding less than the equivalent amount of a manganese salt to a solution of the ligand in the complexing step.
Accordingly, this invention relates to a process for washing and cleaning and also for preventing the reabsorption of migrating dyes in a washing liquor, which process comprises adding to the washing liquor comprising a peroxide-containing washing agent 0.5 to 150 mg, preferably 1.5 to 75 mg, more preferably 1.5 to 30 mg, per liter of washing liquor of a mixture consisting of 2 to 85% by weight of a manganese complex and of 98 to 15% by weight of an organic ligand which can form a complex with manganese, the percentages being based on the entire weight of the mixture.
Manganese complexes suitable for the process of this invention are in particular compounds of formula 
wherein
A is a anion;
n is 0, 1, 2 or 3,
m is 0, 1, 2 or 3,
R4 is hydrogen or linear or branched C1-C4alkyl,
R8 is hydrogen or linear or branched C1-C4alkyl,
Y is a linear or branched alkylene radical of formula xe2x80x94[C(R4)2]rxe2x80x94, wherein r is an integer from 1 to 8 and the R4 groups have each independently of one another the meanings cited above;
xe2x80x94CXxe2x95x90CXxe2x80x94, wherein X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)amino,
xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94, wherein R4 has the meaning cited above, and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of formula: 
xe2x80x83or a 1,2-aryl radical of formula 
wherein
R9 is hydrogen, SO3H, CH2OH or CH2NH2,
R and R1 are each independently of the other cyano, halogen, OR4 or COOR4, wherein R4 has the meaning cited above, nitro, linear or branched C1-C8alkyl, linear or branched partially fluorinated or perfluorinated C1-C8alkyl, NR5R6, wherein R5 and R6 are identical or different and are each hydrogen or linear or branched C1-C12alkyl, or linear or branched C1-C8alkyl-R7, wherein R7 is NH2, OR4, COOR4 or NR5R6, which have the meanings cited above, or xe2x80x94CH2xe2x80x94N⊕R4R6R7, or -N⊕R4R5R6, wherein R4, R5 and R6 have the meanings cited above, R2 and R3 are each independently of the other hydrogen, linear or branched C1-C4alkyl or unsubstituted aryl, or aryl which is substituted by cyano, halogen, OR4 or COOR4, wherein R4 is hydrogen or linear or branched C1-C4alkyl, by nitro, linear or branched C1-C8alkyl, NHR5 or NR5R6, wherein R5 and R6 are identical or different and are each hydrogen or linear or branched C1-C12alkyl, or by linear or branched C1-C8alkyl-R7, wherein R7 is NH2, OR4, COOR4 or NR5R6, which have the meanings cited above, or by xe2x80x94N⊕R4R5R6, wherein R4, R5 and R6 have the meanings cited above.
If, in the compounds of formula (1), R and/or R1 are defined as xe2x80x94N⊕R4R5R6 or xe2x80x94CH2xe2x80x94N⊕R4R6R7 or R2 and/or R3 are defined as aryl which is substituted by xe2x80x94N⊕R4R5R6 or xe2x80x94CH2xe2x80x94N⊕R4R6R7, wherein R4, R5 and R6 have the meanings cited above, then suitable anions for balancing the positive charge at the xe2x80x94N⊕R4R5R6 or xe2x80x94CH2xe2x80x94N⊕R4R6R7 group are halides, such as chloride, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, acetate, tosylate or triflat. Bromide and chloride are preferred.
In those compounds of formula (1) wherein n is 2 or 3, the R groups may have the same or different meanings. The same applies to the compounds of formula (1), wherein m is 2 or 3, with respect to the R1 groups.
Y defined as a 1,2-cyclohexylene radical may be in any of its stereoisomeric cis/trans forms.
Y is preferably a radical of formula xe2x80x94(CH2)rxe2x80x94, wherein r is an integer from 1 to 8, or of formula xe2x80x94C(R4)2xe2x80x94(CH2)pxe2x80x94C(R4)2xe2x80x94, wherein p is a number from 0 to 6, preferably from 0 to 3, and the R4 groups are each independently of one another hydrogen or C1-C4alkyl, preferably hydrogen or methyl, or a 1,2-cyclohexylene radical or a 1,2-phenylene radical of formula: 
Halogen is preferably chloro, bromo or fluoro. Chloro is particularly preferred.
If n or m is 1, the R and R1 groups are preferably in 4-position of the respective benzene ring unless R or R1 is nitro or COOR4. In this case the R or R1 group is preferably in 5-position. If R or R1 is N⊕R4R5R6, the R or R1 group is preferably in 4- or 5-position.
If n or m is 2, the two R or R1groups are preferably in 4,6-position of the respective benzene ring unless R or R1 are nitro or COOR5. In this case the two R or R1 groups are preferably in 3,5-position.
If R or R1 are di(C1-C12alkyl)amino, the alkyl group may be straight-chain or branched. This group preferably contains 1 to 8 carbon atoms, more preferably 1 to 3 carbon atoms.
R and R1 are preferably hydrogen, chloro, OR4, COOR4, N(R4)2 or N⊕(R4)3, wherein in N(R4)2 or N⊕(R4)3 the R4 groups may be different and are hydrogen or C1-C4alkyl, preferably methyl, ethyl or isopropyl.
R2 and R3 are preferably hydrogen, methyl, ethyl or unsubstituted phenyl.
Aryl is typically naphthyl or, preferably, phenyl.
Suitable anions A are, for example, halides such as chloride or bromide, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, acetate, tosylate or triflat. Chloride, bromide and acetate are preferred.
Suitable organic ligands used in the novel mixtures of a manganese complex and an organic ligand are preferably compounds of formula 
wherein R, R1, R2, R3, R4, R8, Y, n and m have the meanings cited for formulae (1) and (2).
The preferred definitions of R, R1, R2, R3, R4, R8, Y, n and m given for the manganese complexes of formula (1) and (2) are also preferred in the case of the ligands of formula (3) and (4).
Other compounds suitable for use as organic ligands in the novel mixtures are those of formula 
wherein R, R2, R8 and n have the meanings cited for formulae (1) and (2).
The preferred definitions of R, R2, R8 and n given for the manganese complexes of formulae (1) and (2) are also preferred in the case of the ligands of formula (5) and (6).
The compounds of formula (1)-(6) are known or can be prepared in a manner known per se. The manganese complexes are prepared, for example, from the corresponding ligands (2) and (3) and a manganese compound. Such methods of preparation are described, inter alia, in U.S. Pat. Nos. 5,281,578 and 4,066,459 and in Bernardo et al., Inorg. Chem. 45 (1996) 387.
The compounds of formula (1) or (2) can be used singly or in admixture with two or more additional compounds of formula (1) or (2). Likewise, the ligands of formulae (3) to (6) can be used singly or in admixture with two or more additional ligands.
The ratio   V  =                                                        entire              ⁢                              xe2x80x83                            ⁢              amount              ⁢                              xe2x80x83                            ⁢              of              ⁢                              xe2x80x83                            ⁢              the                        ⁢                          xe2x80x83                                                                        manganese            ⁢                          xe2x80x83                        ⁢            complexes            ⁢                          xe2x80x83                        ⁢            in            ⁢                          xe2x80x83                        ⁢            the            ⁢                          xe2x80x83                        ⁢            mixture                                      entire      ⁢              xe2x80x83            ⁢      amount      ⁢              xe2x80x83            ⁢      of      ⁢              xe2x80x83            ⁢      the      ⁢              xe2x80x83            ⁢      organic      ⁢              xe2x80x83            ⁢      ligands      ⁢              xe2x80x83            ⁢      in      ⁢              xe2x80x83            ⁢      the      ⁢              xe2x80x83            ⁢      mixture      
in the mixtures used according to this invention is preferably from 0.02 to 5, more preferably from 0.02 to 1. The amounts are based on molar amounts.
This invention also relates to a washing agent, which comprises
I) 5-90%, preferably 5-70%, A) of an anionic surfactant and/or B) of a nonionic surfactant,
II) 5-70%, preferably 5-50%, more preferably 5-40%, C) of a builder substance,
III) 0.1-30%, preferably 1-12%, D) of a peroxide, and
IV) 0.005-2%, preferably 0.02-1%, more preferably 0.05-0.5%, E) of a mixture of a manganese complex of formula (1) or (2) and an organic ligand of formula (3), (4), (5) or (6), the percentages being by weight, based on the entire weight of the washing agent.
It is possible to mix the manganese complexes and the organic ligands first and then to mix the resulting mixture E) with the other washing agent components A), B), C) and D). However, it is also possible to mix the manganese complexes and the organic ligands individually with the remaining washing agent components A), B), C) and D).
The washing agent may be in solid or in liquid form, for example in the form of a liquid non-aqueous washing agent, comprising not more than 5% by weight, preferably from 0 to 1% by weight of water, and as basis a suspension of a builder substance in a nonionic surfactant, as is described e.g. in GB-A-2,158,454.
Preferably, however, the washing agent is obtained in powdered or granulated form.
The washing agent may be produced, for example, by first preparing a starting powder by spray-drying an aqueous slurry, containing all of the above-cited components except the components D) and E), and then adding the dry components D) and E) and mixing all of these components.
It is also possible to add the component E) to an aqueous slurry containing the components A), B) and C) and, after spray-drying this mixture, mixing the component D) with the dry mixture.
It is also possible to start from an aqueous slurry which contains the components A) and C), but not, or only partially, component B). After spray-drying the slurry, the component E) is mixed with the component B) and added thereto, and the component D) is then admixed in dry form.
The anionic surfactant A) may be, for example, a sulfate, sulfonate or carboxylate surfactant, or a mixture thereof.
Preferred sulfates are those which contain 12-22 carbon atoms in the alkyl radical, optionally in combination with alkylethoxysulfates, the alkyl radical of which contains 10-20 carbon atoms.
Preferred sulfonates are, for example, alkylbenzenesulfonates containing 9-15 carbon atoms in the alkyl radical.
The cation in the anionic surfactants is preferably an alkali metal cation, most preferably sodium.
Preferred carboxylates are alkali metal sarcosinates of formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1, wherein R is alkyl or alkenyl containing 8-18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl, and M1 is an alkali metal.
The nonionic surfactant B) may be, for example, a condensate of 3-8 mol of ethylene oxide with 1 mol of primary alcohol containing 9-15 carbon atoms.
Suitable builder substances C) are, for example, alkali metal phosphates, preferably tripolyphosphates, carbonates or bicarbonates, more preferably their sodium salts, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates), or mixtures of these compounds.
Particularly suitable silicates are the sodium salts of crystalline sheet silicates of formula NaHSitO2t+1.pH2O or Na2SitO2t+1.pH2O, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
Preferred aluminium silicates are those which are commercially available under the names Zeolite A, B, X and HS, and also mixtures comprising two or more of these components.
Preferred polycarboxylates are the polyhydroxycarboxylates, in particular citrates, and acrylates as well as their copolymers with maleic anhydride.
Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediaminedisuccinate both in racemic form and in the enantiomerically pure S,S-form.
Particularly suitable phosphonates or aminoalkylenepoly(alkylenephosphonates) are the alkali metal salts of the 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.
Suitable peroxide components D) are, for example, the organic and inorganic peroxides which are known in the literature and available on the market, which bleach textile materials at the standard washing temperatures, for example from 10 to 95xc2x0 C.
The organic peroxides are, for example, mono- or polyperoxides, preferably organic peracids or the salts thereof, such as phthalimidoperoxycapronic acid, peroxybenzoic acid, diperoxydodecane diacid, diperoxynonane diacid, diperoxydecane diacid, diperoxyphthalic acid or the salts thereof.
However, it is preferred to use inorganic peroxides, for example persulfates, perborates, percarbonates and or persilicates. It is of course also possible to use mixtures of inorganic and/or organic peroxides. The peroxides can be obtained in different crystal forms and may have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
The peroxides are preferably added to the washing agent by mixing the components, for example by means of a screw feeding system and/or a fluidised bed mixer.
In addition to the novel combination, the washing agents may contain one or more than one fluorescent whitening agent, for example from the class of the bis-triazinylaminostilbenedisulfonic acid, bis-triazolylstilbenedisulfonic acid, bis-styrylbiphenyl or bis-benzofuranylbiphenyl, a bis-benzoxazolyl derivative, bis-benzimidazolyl derivative, coumarine derivative or a pyrazoline derivative.
The washing agents may also contain suspending agents for dirt, e.g. sodium carboxymethylcellulose, pH-regulators, e.g. alkali or alkaline earth metal silicates, foam regulators, e.g. soaps, salts for regulating the spray-drying and the granulation properties, e.g. sodium sulfate, fragrances and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaches, pigments and/or shading agents. These components must, of course, be stable against the bleaching agent used.
Other additives preferably added to the novel washing agents are polymers which prevent staining during the washing of the textiles through dyes that are present in the washing liquor and that have separated from the textiles under the washing conditions. These polymers are preferably polyvinylpyrrolidones, which are unmodified or modified through the incorporation of anionic or cationic substituents, in particular those having a molecular weight in the range from 5000 to 60000, more preferably from 10000 to 50000. These polymers are preferably used in an amount of 0.05 to 5% by weight, more preferably of 0.2 to 1.7% by weight, based on the entire weight of the washing agent.
The washing agents may additionally contain so-called perborate activators, such as TAED or TAGU. TAED is preferred and is preferably used in an amount from 0.05 to 5% by weight, more preferably from 0.2 to 1.7% by weight, based on the entire weight of the washing agent.
The following non-limitative Examples illustrate the invention in more detail. Parts and percentages are by weight, unless otherwise stated.